Paint and tile base



Patented Nov. 21, 1939 PAINT AND TILE BASE- Frank W. Corkery, Grafton,Pa.

No Drawing. Application June 18, 1937,

. Serial No. 148,962

2 Claims. (Cl. 260-23) This invention relates to a paintand tile basecomprising a drying oil or a mixture of drying oils oxidized inadmixture withan unsaturated oil derived from coal.

Specifically, I have discovered that a mixed oxidized oil having manyuseful qualities may be produced by oxidizing in admixture one or moreof the drying oils, such as linseed oil, China-wood oil, rapeseed oil,and the coal-derived oil which I herein term dipolymer oil. is ofcycliccomposition, and has its more proximate derivation in the lightoil which is distilled over in the by-product coking of coal, or thelight oil which is distilled from the tar of by-product coking, andpurified by the removal of tarry acids and bases. The immediatederivation of the dipolymer oil is either from still residue producedresidually in the fractionation and purification of light oil in theproduction of solvent naphthas, benzol, toluol, or the like, or isproduced by polymerization conducted in crude heavy solvent naphtha.Briefly todiscuss the still residue from which dipolymer oil may beobtained, such still residue may be produced from the fractionation oflight oil in initial, orv crude, stills; may be obtained as a residue.of distillation after acid purification and neutralization of the lightoil or light oil fractions; or may be obtained as bottoms in the stillsby which a fractionation into No. 1 crude solvent naphtha (xylol) andNo. 2 crude heavy solvent naphtha is efiected. It is usually a mixturefrom all these sources, and is in degree contaminated by sulphates andsulphonates.

The various still residues, because of the heat treatment, or acidpurification treatment, or both of such treatments, to which the lightoil is subjected, comprise a large percentage of polymers of the lightoil unsaturates, such as coumarone, indene and styrene, in varyingproportions. While some of such polymers are in a stage ofpolymerization which forms solid resin, others are in the form ofdimers, and it is the dimers of the polymerizable reactives of the lightoil which largely constitute dipolymer oil as derived from stillresidue. from the still residue, the still residue is sub jected todistillation. Distillation desirably may be conducted under asubatmospheric pressure of 20 inches of mercury, and with steam, at astill temperature of about 550 F. If naphthalene and hydrocarbons ofsolvent grade are present these are first distilled off, and thedipolymer oil then comes over as the still temperature is increased tothe point at which distillation This dipolymer oil To recover thedipolymer oil v to a solid residuum is efiected. This dipolymer oil isreadily condensed and'recovered.

Dipolymer oil is also produced by polymerization in crude heavy solventnaphtha, or equivdrip oil, or the like, by some polymerization proc-'ess of the same type as that which produces solid coumarone type resin.In accordance with the conditions of the polymerization process, agreater or lesser-proportion of the polymerizable resin-formingreactives remain in the first stage of polymerization as dimers to formdipolymer oil, and is separated by steam distillation from the higherpolymers forming solid resin. A large proportion of the reactivespresent go to form dipolymer oil if the conditions of the polymerizationprocess be such that a very moderate catalytic effect is exerted duringthe polymerization process. 1

The dipolymer oil with which I am herein concerned may be obtained ineither manner as above described, or may be a mixture of dipolymer oilobtained from still residue and dipolymer oil obtained from apolymerization process conducted in crude solvent naphtha, 'oritsequivalent.

Initially, I may state that I have discovered dipolymer oil to be aneffective solvent for the gel structures produced by oxidation of dryingoils, and that it is capable of dispersing very high gel structures ofthat type. Also, I have discovered that by oxidizing in admixture dryingoil and dipolymer oil, a simple process of oxidation may he employed tocarry the oil to an extremely high gel structure which would be unoil issubjected in a treating vessel to a dispersion of air or, if desired,oxygen in greater or lesser condition of purity, forced under pressurethrough the mixture of oils. Desirably the oil mixture is raised to atemperature of about 175 F. to facilitate the passage of air or oxygen,and

may be maintained approximately constant throughout the process ofoxidation. In utilizing dipolymer oil as the gel-dispersing ingredientpressure fora foot head of the mixed oil, an r of the composition,rather than still residue as disclosed in my co-pending applicationabove noted, I am able to continue oxidation to a high stage withoutincrease ,in temperature.

If, as is desirable, air be utilized as the oxidizing agent, and if itbe supplied for dispersion through the mixed oils in good volume andunder an adequate pressure, such as a 5 pound oxidizing treatment for 5days serves to increase the viscosity of the mixture from about 100Saybolt seconds at 210 F. to about 1000 Saybolt seconds at 210 F. Afteroxidation has reached such stage, increase in viscosity becomesrelatively rapid. Thus I have found that a treating period of 6 daysraises the viscosity of the mixed oil from 100 Saybolt seconds to 1700Saybolt seconds, both at 210 F. Similarly, after 7 days of oxidizingtreatment the viscosity approximates 3000; after 8 days of oxidizingtreatment the viscosity aproximates 5000; and after 9 days of oxidizingtreatment the oil mixture has a viscosity of 10,000 Saybolt seconds at210 F. The exemplary treatment given is conducted without the use of anycatalyst and with ordinary atmospheric air. Some slight advantage may beobtained by replacing air with oxygen, although I have not found thatthe saving in time compensates for the increased cost of the gas. Thetime may be greatly shortened by. use ofan appropriate catalyst, such aslead, manganese, or

cobalt salts in suitable oil-soluble form.

It should be particularly noted that, in a drying oil, a gel structureas high as that represented by a viscosity of 10,000 Saybolt seconds at210 F. cannot be commercially produced by a simple blowing operation,conducted upon the oil by itself; and that such product if it be formedby blowing cannot, because of its lack of thermoplasticity, be readilyremoved from the treating vessel.

The product obtained by oxidizing together a drying oil or mixture ofdrying oils and dipolymer oil is light in color, is clear andtransparent, having a reddish cast, and may be caused to flow whenheated to a moderate temperature. For example, at a viscosity of 10,000Saybolt seconds the product is a solid at normal room temperature, buthas no definite melting point. The outstanding characteristic of thecomposition is the high ,gel structure, which is developed in a simpleand commercial manner, and which renders the pitchy product particularlyvaluable as a component of a binder composition for mastic tile,linoleum, and the like. Because of the high gel structure possessed bythe composite product of oxidation, it may be combined in relativelygreat proportion with a tile resin without unduly lowering themelting-point of the composition, and therefore in conjunction with asuitable resin tends to give a tile binder' composition of highelasticity combined with a high meltingpoint. i

It has been noted in my application, to which reference has been madeabove, and also my co-pending application Serial No. 130,908, filedMarch 15, 1937 issued as Patent No. 2,135,428, that the oxidation ofstill residue from the treatment of coke-oven light'oil and a drying oilin admixture gives a pitch-like product, or synthetic pitch, which is ofa color so much lighter than that of the by-product pitches of animal,vegetable, or marine origin, that it may with increased satisfaction andeconomy be utilized in tile and linoleum, pigmented in lighter shades,

, or it may be more lightly pigmented. Whereas such natural pitches arevery dark, and a synthetic pitch produced by oxidizing drying oil andstill residue in admixture has a color intensity approximating what isknown .on the coal tar color scale as a No. 10 to No. 12 color, thepitchlike product which I obtain by oxidizing together dipolymer oil anddrying oil has a color intensity of about 6 to 8 on the coal tar resincolor scale. In its color it is therefore to be considered animprovement upon a synthetic pitch as produced from still residue,permitting the use of a darker resin asthe resin component of a tilebinder composition, or, conversely, lessening the quantity ofpigmentnecessarily used in making mastic tile or linoleum which is whiteor which is pigmented in light shades.

When the oxidizing treatment is discontinued at such point that the.mixed oil is of lower viscosity, such as a viscosity of from 500 Sayboltseconds to 2000 Saybolt seconds, both at 210 F., it is useful in heavyduty coatings, caulking compounds, and as a component of marine engineoil to promote adhesion of a lubricating oil to surfaces which are wetwith water. It may also be used for numerous other purposes, for example, as a content of putties, inks, adhesives and the like, and forgeneral plasticizing purposes.

The relative proportions of the dipolymer oil and the drying oil may bevaried at will, unless the mixture is to be carried to such viscositythat an extremely high gel structure is developed in the drying oil. Ihave found that an inclusion of dipolymer oil in a proportion of from40% to 50% the weight of the oil mixture is sufficient so to-dispersethe highly oxidized drying oil, that the mixture may without difflcultybe carried to viscosities of 10,000 Saybolt'seconds at 210 F., andabove. An increased proportion of dipolymer oil is useful when oxidizingto extreme viscosities, such as viscosities of the order of 20,000 to30,000 Saybolt seconds at 210 F.

Further to define the dipolymer oil, which I oxidize in admixture with adrying oil, or oils, it is an oily substance, composed largely of thedimers of'the light oil unsaturates (such as coumarone, indene, andpossibly styrene), high boiling cyclic oils, and reaction products ofthe various primary oomponents. It has a specific gravity of about 1.055at F. It has a viscosity of about 100 Saybolt seconds at 210 F., and aviscosity of about 270 Saybolt seconds at 100 F.

Preponderantly it boils within the approximate range of 300 C. to 370C., and a large part of its weight distills close to 340 C, As initiallyproduced, it is of a pale yellow color, and is nonvolatile at ordinarilyencountered temperatures.

Further to consider the proportioning of the drying oil, and thedipolymer oil, it should be understood that the drying oils vary in gelstructure development and thatit is not'possible to give a definitelower limit of dipolymer oil inclusion adequate to carry the oil to aparticular viscosity by serving to disperse. the gel structure of thedrying oil. Thus rape seed oil, sunflower seed oil, soya bean oil, andfish oil are examples of drying oils which, because of their relativelysubstantial content of polymers in stages of soiytion, dipolymer oil maycontain in solution a small percentage of polymers'oi' coumarone and;

indene higher than dimers and still for this pur pose be considered adipolymer oil. It is. however, a fact that in proportion to theirinclusion, the pitchy qualities of the product, such as elasticity; aredecreased. In the higher-viscosity grades of the material it is,therefore, desirable that the proportion of such higher polymers be keptlow in order that the benefits peculiar to the use of dipolymer" oil beto the maximum obtained. In the lower viscosities proposed for use inheavy duty coatings, and the like, the presence of a large proportion ofhigher polymers in the dipolymer" oil may be tolerated.

I cl as my invention: '1. As a material of commerce the herein describedviscous elastic composition suitable-for dene and having by virtue ofireedom from any merization higher than that oi the dimers elasticity inhigh order and no definite melting point, the said material consistingin substantial proportion of its oxidized aromatic initially oilycomponent and being solid at normal room temperature. V i

' 2- As a material of commerce the herein described viscous elasticcomposition suitable for use in association with a resin in a bindercomposition ior mastic tile which is solid atnormal room temperaturehaving a viscosity from about 2000- to as much as 10,000 Saybolt secondsat 210 F. and having a color intensity below a No.

-' 10 color on the waiter resin color scale; said composition consistingof a self-compatible oxidized mixture of an oxidizable drying oil and anoily aromatic substance composed preponderantiy oi the dimers ofcoumarone and indene and having by'vlrtue of freedom from anysubstantial content of polymers in stages of polymerization higher thanthat of the dimers elas ticity of high order and no definite-meltingpoint;

the said material consisting in substantial pro-,

aromatic initially oily 25 portion of its oxidized component. FRANK W.CORKERY.

